Industrial processes for the production of mixtures of cyclohexanol and cyclohexanone from cyclohexane are currently of considerable commercial significance and are well described in the patent literature. In accordance with typical industrial practice, cyclohexane is oxidized to form a reaction mixture containing cyclohexyl hydroperoxide (CHHP). The resulting CHHP is decomposed, optionally in the presence of a catalyst, to form a reaction mixture containing cyclohexanol and cyclohexanone. In the industry, such a mixture is known as a K/A (ketone/alcohol) mixture, and can be readily oxidized to produce adipic acid, which is an important reactant in processes for preparing certain condensation polymers, notably polyamides. Due to the large volumes of adipic acid consumed in these and other processes, improvements in processes for producing adipic acid and its precursors can be used to provide beneficial cost advantages.
Druliner et al., U.S. Pat. No. 4,326,084, disclose an improved catalytic process for oxidizing cyclohexane to form a reaction mixture containing CHHP, and for subsequently decomposing the resulting CHHP to form a mixture containing K and A. The improvement involves the use of certain transition metal complexes of 1,3-bis(2-pyridylimino)isoindolines as catalysts for cyclohexane oxidation and CHHP decomposition. According to this patent, these catalysts demonstrate longer catalyst life, higher CHHP conversion to K and A, operability at lower temperatures (80-160.degree. C.), and reduced formation of insoluble metal-containing solids, relative to results obtained with certain cobalt(II) fatty acid salts, e.g., cobalt 2-ethylhexanoate.
Druliner et al., U.S. Pat. No. 4,503,257, disclose another improved catalytic process for oxidizing cyclohexane to form a reaction mixture containing CHHP, and for subsequently decomposing the resulting CHHP to form a mixture containing K and A. This improvement involves the use of Co.sub.3 O.sub.4, MnO.sub.2, or Fe.sub.3 O.sub.4 applied to a suitable solid support as catalysts for cyclohexane oxidation and CHHP decomposition at a temperature from about 80.degree. C. to about 130.degree. C., in the presence of molecular oxygen.
Sanderson et al., U.S. Pat. No. 5,414,163, disclose a process for preparing t-butyl alcohol from t-butyl hydroperoxide in the liquid phase over catalytically effective amounts of titania, zirconia, or mixtures thereof.
Sanderson et al., U.S. Pat. Nos. 5,414,141, 5,399,794 and 5,401,889, disclose a process for preparing t-butyl alcohol from t-butyl hydroperoxide in the liquid phase over catalytically effective amounts of palladium with gold as a dispersing agent supported on alumina.
Druliner et al., U.S. provisional application No. 60/025,368 filed Sep. 3, 1996 (now PCT US97/15332 filed Sep. 2, 1997), disclose decomposing a hydroperoxide by contacting it with a catalytic amount of a heterogenous catalyst of Zr, Nb, Hf and Ti hydroxides or oxides. Preferably, the catalyst is supported on SiO.sub.2, Al.sub.2 O.sub.3, carbon or TiO.sub.2.
Further improvements and options are needed for hydroperoxide decomposition to K/A mixtures in order to overcome the deficiencies inherent in the prior art. Other objects and advantages of the present invention will become apparent to those skilled in the art upon reference to the detailed description which hereinafter follows.